Method for producing bisphenol catalysts and bisphenols

ABSTRACT

This disclosure relates to a method for producing and using catalysts in the production of bisphenols, and in particular to a method for producing catalysts which contain poly-sulfur mercaptan promoters, and using these catalysts in the production of bisphenol-A and its derivatives.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.09/954,909, now U.S. Pat. No. 6,620,939, filed Sep. 18, 2001, the entirecontents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

This disclosure relates to a method for producing and using catalystsfor the production of bisphenols, and in particular to a method forproducing catalysts which contain attached poly-sulfur mercaptanpromoters, and using these catalysts in the production of bisphenol-A,and its derivatives.

Typical bisphenols, such as 4,4′-isopropylidenediphenol, e.g.,bisphenol-A (BPA), are widely employed as monomers in the manufacture ofpolymeric materials, such as engineering thermoplastics. For example,BPA is a principal monomer used in the manufacture of polycarbonate.Bisphenols are generally prepared by the electrophilic addition ofaldehydes, or ketones such as acetone, to aromatic hydroxy compoundssuch as phenol, in the presence of an acidic catalyst compositions.These types of reactions are also referred to as acid catalyzedcondensation reactions. Commercially, sulfonated polystyrene resincross-linked with divinylbenzene, e.g., PS-DVB, is typically used as asolid acid component of the catalyst composition. Reaction promoters canalso be employed as part of a catalyst composition to improve thereaction rate, and selectivity, of the desired condensation reaction; inthe case of BPA, the desired selectivity is for the para-para isomer(pp-BPA). Promoters can be present as unattached molecules in the bulkreaction matrix, e.g., “bulk-promoters”, or can be attached to the resinthrough ionic linkages, e.g., “attached-promoters”. A useful class ofpromoter is the mercaptans, specifically thiols, e.g., organosulfurcompounds which are derivatives of hydrogen sulfide. Typical mercaptanpromoters contain only a single sulfur atom, and result in catalystcompositions that catalyze bisphenol formation with poor isomerselectivity; in the case of BPA, the undesired selectivity if for theortho-para isomer (op-BPA). Consequently, a long felt yet unsatisfiedneed exists for new and improved catalyst compositions, and a method toproduce them, which are selective in the production of bisphenols.Herein, a method to produce catalyst compositions comprising poly-sulfurmercaptan promoters is disclosed. The use of poly-sulfur mercaptanpromoters results in catalyst compositions that are highly selective inthe formation of bisphenols.

SUMMARY OF THE INVENTION

In one embodiment, the present disclosure pertains to a method forproducing a catalyst composition which catalyzes the formation ofbisphenols from aromatic hydroxy compounds and carbonyl containingcompounds, said method comprising the step of attaching a poly-sulfurmercaptan promoter component to a solid acid support componentcomprising a protic acid functionality, said poly-sulfur mercaptanpromoter component having the following structure (I),

wherein R₁ is a functionality selected from the group consisting of apositively charged ammonium functionality, a positively chargedguanidinium functionality, a positively charged phosphoniumfunctionality, and a neutral amine;

-   wherein a is between about 0 and about 11;-   wherein b is between about 1 and about 11;-   wherein c is between about 1 and about 11;-   wherein d is between about 1 and about 5;-   wherein X is a linking functionality which is one member selected    from the group consisting of a linear aliphatic chain comprising    between about 1 and about 11 carbon atoms, a cyclic aliphatic ring    comprising at least 5 carbon atoms, a cyclic aromatic ring    comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle    comprising at least 3 carbon atoms, and a cyclic aromatic    heterocycle comprising at least 3 carbon atoms;-   wherein Y is a linking functionality which is one member selected    from the group consisting of a linear aliphatic chain comprising    between about 1 and about 11 carbon atoms, a cyclic aliphatic ring    comprising at least 5 carbon atoms, a cyclic aromatic ring    comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle    comprising at least 3 carbon atoms, and a cyclic aromatic    heterocycle comprising at least 3 carbon atoms; and-   wherein R₂ is one member selected from the group consisting of a    hydrogen, a tertiary aliphatic functionality, an ester    functionality, a carbonate functionality, and a benzyl functionality    which is attached via the benzylic methylene carbon.

In another embodiment, the present disclosure relates to a method forforming bisphenols, comprising the step of reacting an aromatic hydroxycompound with a carbonyl containing compound in the presence of acatalyst composition, said catalyst composition comprising a solid acidcomponent and a poly-sulfur mercaptan promoter component having thefollowing structure (I),

-   wherein R₁ is a functionality selected from the group consisting of    a positively charged ammonium functionality, a positively charged    guanidinium functionality, a positively charged phosphonium    functionality, and a neutral amine;-   wherein a is between about 0 and about 11;-   wherein b is between about 1 and about 11;-   wherein c is between about 1 and about 11;-   wherein d is between about 1 and about 5;-   wherein X is a linking functionality which is one member selected    from the group consisting of a linear aliphatic chain comprising    between about 1 and about 11 carbon atoms, a cyclic aliphatic ring    comprising at least 5 carbon atoms, a cyclic aromatic ring    comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle    comprising at least 3 carbon atoms, and a cyclic aromatic    heterocycle comprising at least 3 carbon atoms;-   wherein Y is a linking functionality which is one member selected    from the group consisting of a linear aliphatic chain comprising    between about 1 and about 11 carbon atoms, a cyclic aliphatic ring    comprising at least 5 carbon atoms, a cyclic aromatic ring    comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle    comprising at least 3 carbon atoms, and a cyclic aromatic    heterocycle comprising at least 3 carbon atoms; and-   wherein R₂ is one member selected from the group consisting of a    hydrogen, a tertiary aliphatic functionality, an ester    functionality, a carbonate functionality, and a benzyl functionality    which is attached via the benzylic methylene carbon.

DETAILED DESCRIPTION

The present disclosure is directed to a method for producing and usingcatalysts for the production of bisphenols, and is suitable for thepreparation of attached-promoter catalysts, which can effectivelycatalyze the formation of bisphenols from aromatic hydroxy compounds andcarbonyl containing compounds. In the context of the present disclosure,the term “catalyst” refers to a composition, wherein the individualconstituents of the composition are referred to as “components”. In thecontext of the present disclosure, a typical catalyst comprises a“support” component that is generally a polymeric material, alsoreferred to as a “resin”, comprising a protic acid functionality, and a“promoter” component that is generally an organic compound. As usedherein, the term “functionality” is defined as an atom, or group ofatoms acting as a unit, whose presence imparts characteristic propertiesto the molecule to which the functionality is attached. In the contextof the present disclosure, a “protic acid functionality” is defined as agroup of atoms that are covalently attached to the polymeric supportcomponent of the catalyst, which can act as a source of protons, e.g., aBrönsted acid, and upon deprotonation the counter-anion can serve as ananionic moiety of an ionic bond with a cationically charged promotercomponent. A suitable example of a support component is a polystyreneresin, cross-linked with up to 12 percent of divinylbenzene. Suitableexamples of protic acid functionalities, which are attached to thesupport component, are a sulfonic acid functionality, which upondeprotonation produces a sulfonate anion functionality, a phosphonicacid functionality, which upon deprotonation produces a phosphonateanion functionality, and a carboxylic acid functionality, which upondeprotonation produces a carboxylate anion functionality. For example,in one embodiment of the present disclosure, the support component is apolystyrene resin, cross-linked with 4% of divinylbenzene, andfunctionalized with sulfonic acid groups.

Promoter components are typically organic compounds, which can readilyform stable cationic species. Typical promoter components comprise atleast one mercaptan chain functionality, and an organic skeletalfunctionality, to which the mercaptan chain functionality is covalentlybound. As used herein, the term “mercaptan chain functionality” isdefined as an organosulfur functionality, which is a derivative ofhydrogen sulfide. In the context of the present disclosure, a typicalmercaptan chain functionality, i.e. —{[(X)_(a)—S]_(b)—(Y)_(c)—S—R},comprises at least two (2) sulfur atoms. In one embodiment up to twelvesulfur atoms can be present in a single mercaptan chain, e.g., b isbetween about 1 and about 12 in a chain defined by the followingformula, —{[(X)_(a)—S]_(b)—(Y)_(c)—S—R}. The sulfur atoms in a typicalmercaptan chain functionality are linked by various organic linkersfunctionalities, e.g., X and Y. In the context of the presentdisclosure, typical linker functionalities include, but are not limitedto, a linear aliphatic chain comprising between about 1 and about 11carbon atoms, a cyclic aliphatic ring comprising at least 5 carbonatoms, a cyclic aromatic ring comprising at least 6 carbon atoms, acyclic aliphatic heterocycle comprising at least 3 carbon atoms, and acyclic aromatic heterocycle comprising at least 3 carbon atoms. The term“organic skeletal functionality” is defined as an organic functionality,which is capable of forming a covalent bond with at least one mercaptanchain functionality, and can form a stable cationic species that can actas a cationic moiety of an ionic bond. Suitable examples of organicskeletal functionalities include, but are not limited to, analkylammonium functionality, an alkylguanidinium functionality, analkylphosphonium functionality, and an amino functionality. Typicallyamino skeletal functionalities include, but are not limited to,monocyclic aromatic amino compounds, and polycyclic aromatic aminocompounds. For example, suitable amino skeletal functionalities include,but are not limited to, pyridyl functionalities, benzimidazolefunctionalities, benzothiazole functionalities, and imidazolefunctionalities. In the case of skeletal functionalities that comprisering systems, a mercaptan chain functionality can be bonded to the ringsystem at any one of the ring locations that is capable of covalentlybonding a substituent. For example, in the case of a pyridyl-mercaptanpromoter, a mercaptan chain functionality can be appended to pyridinering at any one of the 2, 3, or 4 ring positions. Furthermore, in eachof the classes of mercaptan promoter described above, i.e. alkylammoniummercaptans, alkylguanidinium mercaptans, alkylphosphonium mercaptans,and amino mercaptans, more than one mercaptan chain can be present inthe promoter. For example, in the case of pyridyl-mercaptans, thepyridine ring can be substituted with up to 5 mercaptan chainfunctionalities, with one chain covalently bonded to each of the fivecarbon ring positions of the pyridine ring.

Substituent groups, which are typically represented by the symbol R inchemical structures, can also be attached to a promoter to adjust thepromoter's electronic properties, steric properties, and combinationsthereof, to affect the reactivity of the overall catalyst composition.Suitable promoter substituent groups include, but are not limited to, ahydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, ahydroxide, an alkoxide functionality comprising between about 1 andabout 11 carbon atoms, an aryloxide functionality comprising at leastabout 6 carbon atoms, an aliphatic functionality comprising betweenabout 1 and about 11 carbon atoms, and an aromatic functionalitycomprising at least about 6 carbon atoms. In the case of aminomercaptansthat comprise ring systems, a substituent group can also be acycloaliphatic ring comprising at least about 5 carbon atoms, saidcycloaliphatic ring being fused to the amino ring through an adjacentring substituent, or a cycloaromatic ring comprising at least about 6carbon atoms, said cycloaromatic ring being fused to the amino ringthrough an adjacent ring substituent.

Attachment of a promoter component to the polymeric support component istypically made via an ionic linkage between a cationically chargedpromoter component, which in the case of an aminomercaptan results fromthe protonation at the nitrogen atom, and the anionically chargeddeprotonated acid functionality on the resin backbone. The attachment ofan aminomercaptan promoter to an acid functionalized polymeric supportcan be performed in an aqueous solution. Herein, the term “aqueoussolution” includes those solutions where water is present as a solvent.For example, a protected mercaptan promoter, such as[2-((CH₂)₂—S—(CH₂)₃—S—(^(t)—Bu))pyridine], can be attached to a sulfonicacid functionalized PS-DVB resin through an ionic linkage formed betweena [2-((CH₂)₂—S—(CH₂)₃—S—(^(t)—Bu))pyridinium]⁺ cation, and a sulfonateanion on the polymeric support, by mixing the PS-DVB resin and themercaptan promoter together in water. Alternatively, the aminomercaptanpromoter can be attached to an acid functionalized polymeric support inan organic medium comprising an aromatic hydroxy compound, such asphenol.

In one embodiment of the present disclosure, the mercaptan promoter isprotected at the sulfur atom, before it is attached to the support witha typical protecting group functionality used to protect Group 16elements, such as oxygen and sulfur, from oxidation. As used herein, theterm “protecting group” refers to a functionality which inhibits aspecific type of reactivity, and in the context of the presentdisclosure, the protecting group attached to the terminal sulfur atom ofthe mercaptan promoter is present in order to inhibit the oxidation ofthe terminal sulfur atom; typically, unprotected mercaptan sulfhydrylgroups are readily oxidized to disulfides, or more highly oxidizedgroups, during synthesis or under the conditions in which the promotersare attached to the polymeric supports. In the context of the presentdisclosure, suitable examples of sulfur protecting groups include, butare not limited to, aliphatic functionalities that form stablecarbocations, ester functionalities, carbonate functionalities, andbenzylic functionalities. When used in conjunction with the termprotecting group, the term “aliphatic” refers to an organic compoundcomposed of hydrogen atoms and carbon atom arranged in a branched chain,capable of forming a stable carbocation species. For example, in oneembodiment the aliphatic protecting group is a tertiary butyl group,e.g., —C(CH₃)₃. However, when used in conjunction with the term“substituent”, the term “aliphatic” refers more broadly to an organiccompound composed of hydrogen atoms and carbon atoms which containsbetween about 1 and about 11 carbon atoms, arranged in either a linearor branched chain. Furthermore, when used in conjunction with the term“substituent”, the term “aromatic” is defined as an organic compoundcomposed of hydrogen atoms and carbon atoms, which contains at leastabout 6 cyclic conjugated carbon atoms.

Suitable examples of ester functionalities, e.g., —C(O)R wherein R canbe either an aliphatic substituent or an aromatic substituent, includethose esters which contain between about 1 and about 11 carbon atoms,such as an acetate group, e.g., —C(O)CH₃. Suitable examples of carbonatefunctionalities, e.g., —C(O)OR, include carbonates with aliphaticsubstituents or aromatic substituents. An example of a suitablealiphatic carbonate protecting group is as a tert-butoxy carbonate,e.g., —C(O)O—^(t)Bu. An example of a suitable aromatic carbonateprotecting group is as a phenyl carbonate group, e.g., —C(O)OPh.Suitable examples of benzylic functionalities, e.g., —CH₂(aryl), includethose benzylic groups which contain at least 7 carbon atoms, such as abenzyl group, e.g., —CH₂(C₆H₆).

In one embodiment, the promotor component is

wherein R₂₄ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon; and wherein ris 3 or 6.

In another embodiment, the promoter component is,

wherein R₂₅ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the beuzylic methylene carbon; and wherein tis 3 or 6.

In yet another embodiment, the promoter component is

wherein R₂₆ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon; and wherein uis 3 or 6.

In yet another embodiment, the promoter component is

wherein R₂₇ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon; and wherein vis 3 or 6.

In yet another embodiment, the promoter component is,

wherein R₂₈ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon; and wherein wis 3 or 6.

In yet another embodiment, the promoter component is

wherein R₂₉ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon; and wherein xis 3 or 6.

In yet another embodiment, the promoter component is,

wherein R₃₀ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon.

In yet another embodiment, the promoter component is,

wherein R₃₁ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon.

In yet another embodiment the promoter component is,

wherein R₃₂ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon.

In yet another embodiment, the promoter component is,

wherein R₃₃ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon; and wherein yis 3 or 6.

In another embodiment, the present application relates to a method forusing the catalysts disclosed herein, to catalyze the formation ofbisphenols, such as 4,4′-isopropylidenediphenol. In the context of thepresent disclosure, the term “catalyze”, when used in reference to acatalyst composition, refers to the facilitation of a specific chemicaltransformation between one or more chemical species, at a reaction rateor selectivity, which is greater than, or equal to, a predeterminedreference reaction rate, or reference selectivity, under a specific setof reaction conditions. In the context of the present disclosure, thereaction that is being catalyzed is a condensation reaction between anaromatic hydroxy compound and carbonyl-comprising compound to form abisphenol, which typically occurs in a liquid reaction mixture. Herein,the term “liquid reaction mixture” is defined as a mixture of compounds,which are present predominantly in a liquid state at ambient roomtemperature and pressure (e.g., about 25° C. and about 0.1 MPa). Liquidreaction mixtures can be homogeneous liquid mixtures composed of one ofmore phases (e.g., biphasic liquid reaction mixtures), or heterogeneousliquid-solid mixtures comprising components that are present in thesolid state (e.g., precipitates).

The components which are present in a typical liquid reaction mixture ofa condensation reaction to produce bisphenols include, but are notlimited to, the desired bisphenol, byproducts of the condensationreaction such as water, and bisphenols other than the desired bisphenol,soluble components of the catalyst composition, insoluble components ofthe catalyst composition, and unreacted starting materials, e.g. anaromatic hydroxy compound, and a carbonyl containing compound. Suitabletypes of aromatic hydroxy compounds include, but are not limited to,monocyclic aromatic compounds comprising at least one hydroxy group, andpolycyclic aromatic compounds comprising at least one hydroxy group.Illustrative examples of suitable aromatic hydroxy compounds include,but are not limited to, phenol, alkylphenols, alkoxyphenols, naphthols,alkylnaphthols, and alkoxynaphthols. As used herein, the term “carbonylcontaining” compounds refers to organic compounds which contain an sp²hybridized carbon which is double bonded to an oxygen atom, and includesaldehydes, and ketones. An example of a suitable aldehyde isacetaldehyde. An example of a suitable ketone is acetone.

The condensation reaction can be influenced by various reactionconditions including, but not limited to, reactor vessel pressure,reaction temperature, agitation rate, the pH of the reaction mixture,catalyst concentration, the weight % of various components of the liquidreaction mixture including, but not limited to, the weight % of anaromatic hydroxy compound, the weight % of a carbonyl containingcompound, the weight % of a desired bisphenol, and the weight % ofwater. For example, typical reaction conditions for the catalyticproduction of BPA using the catalysts described herein and anincremental flow reactor include, but are not limited to, temperaturesbetween about 55° C. and about 85° C., acetone concentrations of betweenabout 1% and about 10%, and space velocities between about 0.1 pounds offeed per pound of solid catalyst per hour and 10 pounds of feed perpound of solid catalyst per hour.

In one embodiment, a method for producing a catalyst composition whichcatalyzes the formation of bisphenols from aromatic hydroxy compoundsand carbonyl containing compounds comprises the step of attaching apoly-sulfur mercaptan promoter component to a solid acid supportcomponent comprising a protic acid functionality, wherein thepoly-sulfur mercaptan promoter component has the following structure(I),

wherein R₁ is a functionality selected from the group consisting of apositively charged ammonium functionality, a positively chargedguanidinium functionality, a positively charged phosphoniumfunctionality, and a neutral amine; wherein a is between about 0 andabout 11; wherein b is between about 1 and about 11; wherein c isbetween about 1 and about 11; wherein d is between about 1 and about 5;wherein X is a linking functionality which is one member selected fromthe group consisting of a linear aliphatic chain comprising betweenabout 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising atleast 5 carbon atoms, a cyclic aromatic ring comprising at least 6carbon atoms, a cyclic aliphatic heterocycle comprising at least 3carbon atoms, and a cyclic aromatic heterocycle comprising at least 3carbon atoms; wherein Y is a linking functionality which is one memberselected from the group consisting of a linear aliphatic chaincomprising between about 1 and about 11 carbon atoms, a cyclic aliphaticring comprising at least 5 carbon atoms, a cyclic aromatic ringcomprising at least 6 carbon atoms, a cyclic aliphatic heterocyclecomprising at least 3 carbon atoms, and a cyclic aromatic heterocyclecomprising at least 3 carbon atoms; and wherein R₂ is one memberselected from the group consisting of a hydrogen, a secondary aliphaticfunctionality, a tertiary aliphatic functionality, an esterfunctionality, a carbonate functionality, and a benzyl functionalitywhich is attached via the benzylic methylene carbon.

In the structure (I) above, the tertiary aliphatic functionality is onemember selected from the group consisting of a branched aliphaticfunctionality, and a cyclic aliphatic functionality. Further, the R₂functionality is one member selected from the group consisting of anisopropyl functionality, an isobutyl functionality, a tertiary butylfunctionality, a tertiary amyl functionality, a cyclopentylfunctionality, a benzyl, a 4-methoxybenzyl functionality, a1-methylcyclohexyl functionality, and a cyclohexyl functionality. Theester functionality is one member selected from the group consisting ofan acetate functionality, a propionate functionality, and a benzoatefunctionality. The carbonate functionality is one member selected fromthe group consisting of an alkyl carbonate functionality, and anaromatic carbonate functionality.

In an exemplary embodiment, the bisphenol which is being formed is4,4′-isopropylidenediphenol. The carbonyl containing compound is aketone or an aldehyde. A preferred carbonyl compound is acetone. Apreferred aromatic hydroxy compound is phenol. It is generally desiredfor the attachment step to be performed in an aqueous solutioncomprising water. In one embodiment, the solid acid in structure (I)comprises at least one member selected from the group consisting ofpolystyrene, a zeolite, and silica. In another embodiment, the solidacid is a sulfonic acid functionalized polymeric acid, wherein thepolymeric resin further comprises divinylbenzene in an amount of up toabout 12 wt % of the total weight of the polymeric resin. In anotherembodiment, the solid acid in structure (I) comprises a protic acidfunctionality having at least one member selected from the groupconsisting of a sulfonic acid functionality, a phosphonic acidfunctionality, and a carboxylic acid functionality.

In one embodiment, a method for producing a catalyst composition whichcatalyzes the formation of bisphenols from aromatic hydroxy compoundsand carbonyl containing compounds comprises the step of attaching apoly-sulfur mercaptan promoter component to a polymeric resin componentcomprising a protic acid functionality. The functionalized poly-sulfurmercaptan promoter may be a pyridine mercaptan having the following thestructure (II),

-   wherein e is between about 0 and about 11; wherein f is between    about 1 and about 11;-   wherein g is between about 1 and about 11; wherein h is between    about 1 and about 5;-   wherein X is a linking functionality which is one member selected    from the group consisting of a linear aliphatic chain comprising    between about 1 and about 11 carbon atoms, a cyclic aliphatic ring    comprising at least 5 carbon atoms, a cyclic aromatic ring    comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle    comprising at least 3 carbon atoms, and a cyclic aromatic    heterocycle comprising at least 3 carbon atoms;-   wherein Y is a linking functionality which is one member selected    from the group consisting of a linear aliphatic chain comprising    between about 1 and about 11 carbon atoms, a cyclic aliphatic ring    comprising at least 5 carbon atoms, a cyclic aromatic ring    comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle    comprising at least 3 carbon atoms, and a cyclic aromatic    heterocycle comprising at least 3 carbon atoms; wherein R₃ is a    hydrogen or a sulfur-protecting functionality which is one member    selected from the group consisting of an aliphatic functionality    comprising at least about 4 carbon atom, an ester functionality    comprising between about 1 and about 11 carbon atoms, a carbonate    functionality comprising between about 1 and about 11 carbon atoms,    and a benzylic functionality comprising at least about 7 carbon    atoms which is attached to the terminal sulfur atom via the benzylic    methylene carbon; and wherein at least one member selected from the    group consisting of R₄, R₅, R₆, R₇, and R₈ is a    {[(X)_(e)S]_(f)[(Y)_(g)S—R₃]} chain, and each of R₄, R₅, R₆, R₇, and    R₈ that is not a {[(X)_(e)S]_(f)[(Y)_(g)S—R₃]} chain is    independently one member selected from the group consisting of a    hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl    group, a hydroxide, an alkoxide functionality comprising between    about 1 and about 11 carbon atoms, an aryloxide functionality    comprising at least about 6 carbon atoms, an aliphatic functionality    comprising between about 1 and about 11 carbon atoms, an aromatic    functionality comprising at least about 6 carbon atoms, a    cycloaliphatic ring comprising at least about 5 carbon, said    cycloaliphatic ring being fused to the pyridine ring through an    adjacent ring substituent, and a cycloaromatic ring comprising at    least about 6 carbon atoms, said cycloaromatic ring being fused to    the pyridine ring through an adjacent ring substituent. In one    embodiment in the structure (II) above, X is a —CH₂— group, e is 2,    f is 1, Y is a —CH₂— group, g is 3, and R₄ is the    {[(X)_(e)S]_(f)[(Y)_(g)S—R₃]} chain in structure. In another    embodiment in the structure (II) above, X is a —CH₂— group, e is 2,    f is 1, Y is a —CH₂— group, g is 3, and R₅ is the    {[(X)_(e)S]_(f)[(Y)_(g)S—R₃]} chain. In yet another embodiment in    the structure (II) above, X is a —CH₂—group, e is 2, f is 1, Y is a    —CH₂— group, g is 3, and R₆ is the {[(X)_(e)S]_(f)[(Y)_(g)S—R₃]}    chain.

In one embodiment, the poly-sulfur mercaptan promoter component is afunctionalized benzimidazole mercaptan, wherein the functionalizedbenzimidazole mercaptan has the structure (III),

wherein i is between about 0 and about 11; wherein j is between about 1and about 11; wherein k is between about 1 and about 11; wherein R₉ is ahydrogen atom or a sulfur-protecting functionality which is one memberselected from the group consisting of an aliphatic functionalitycomprising at least about 4 carbon atom, an ester functionalitycomprising between about 1 and about 11 carbon atoms, a carbonatefunctionality comprising between about 1 and about 11 carbon atoms, anda benzylic functionality comprising at least about 7 carbon atoms whichis attached to the terminal sulfur atom via the benzylic methylenecarbon; wherein R₁₀ is one member selected from the group consisting ofa hydrogen, an aliphatic carbonyl functionality comprising about 1 toabout 11 carbon atoms, an aliphatic functionality comprising betweenabout 1 and about 11 carbon atoms, an aromatic carbonyl functionalitycomprising at least about 7 carbon atoms, and an aromatic functionalitycomprising at least about 6 carbon atoms; and wherein each of R₁₁, R₁₂,R₁₃ and R₁₄ are independently one member selected from the groupconsisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide,a vinyl group, a hydroxide, an alkoxide functionality comprising betweenabout 1 and about 11 carbon atoms, an aryloxide functionality comprisingat least about 6 carbon atoms, an aliphatic functionality comprisingbetween about 1 and about 11 carbon atoms, an aromatic functionalitycomprising at least about 6 carbon atoms, a cycloaliphatic ringcomprising at least about 5 carbon atoms, said cycloaliphatie ring beingfused to the benzimidazole arene ring through an adjacent ringsubstituent, and a cycloaromatic ring comprising at least about 6 carbonatoms, said cycloaromatic ring being fused to the benzimidazole arenering through an adjacent ring substituent.

In another embodiment, the poly-sulfur mercaptan promoter component is afunctionalized benzothiazole mercaptan, wherein the functionalizedbenzothiazole mercaptan has the structure (IV),

-   wherein l is between about 0 and about 11; wherein m is between    about 1 and about 11;-   wherein n is between about 1 and about 11; wherein R₁₅ is a hydrogen    atom or a sulfur-protecting functionality which is one member    selected from the group consisting of an aliphatic functionality    comprising at least about 4 carbon atom, an ester functionality    comprising between about 1 and about 11 carbon atoms, a carbonate    functionality comprising between about 1 and about 11 carbon atoms,    and a benzylic functionality comprising at least about 7 carbon    atoms which is attached to the terminal sulfur atom via the benzylic    methylene carbon; and wherein each of R₁₆, R₁₇, R₁₈, and R₁₉ are    independently one member selected from the group consisting of a    hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl    group a hydroxide, an alkoxide functionality comprising between    about 1 and about 11 carbon atoms, an aryloxide functionality    comprising at least about 6 carbon atoms, an aliphatic functionality    comprising between about 1 and about 11 carbon atoms, an aromatic    functionality comprising at least about 6 carbon atoms, a    cycloaliphatic ring comprising at least about 5 carbon atoms, said    cycloaliphatic ring being fused to the benzothiazole arene ring    through an adjacent ring substituent, and a cycloaromatic ring    comprising at least about 6 carbon atoms, said cycloaromatic ring    being fused to the benzothiazole arene ring through an adjacent ring    substituent.

In another embodiment, the poly-sulfur mercaptan promoter component is afunctionalized imidazole mercaptan, wherein the functionalized imidazolemercaptan has the structure (V),

-   wherein o is between about 0 and about 11; wherein p is between    about 1 and about 11;-   wherein q is between about 1 and about 11; wherein R₂₀ is a hydrogen    atom or a sulfur-protecting functionality which is one member    selected, from the group consisting of an aliphatic functionality    comprising at least about 4 carbon atom, an ester functionality    comprising between about 1 and about 11 carbon atoms, a carbonate    functionality comprising between about 1 and about 11 carbon atoms,    and a benzylic functionality comprising at least about 7 carbon    atoms which is attached to the terminal sulfur atom via the benzylic    methylene carbon; wherein R₂₁ is one member selected from the group    consisting of a hydrogen, an aliphatic carbonyl functionality    comprising about 1 to about 11 carbon atoms; an aliphatic    functionality comprising between about 1 and about 11 carbon atoms,    an aromatic carbonyl functionality comprising at least about 7    carbon atoms, and an aromatic functionality comprising at least    about 6 carbon atoms; and-   wherein each of R₂₂ and R₂₃ are independently one member selected    from the group consisting of a hydrogen, a fluoride, a bromide, a    chloride, an iodide, a vinyl group, a hydroxide, an alkoxide    functionality comprising between about 1 and about 11 carbon atoms,    an aryloxide functionality comprising at least about 6 carbon atoms,    an aliphatic functionality comprising between about 1 and about 11    carbon atoms, an aromatic functionality comprising at least about 6    carbon atoms, a cycloaliphatic ring comprising at least about 5    carbon atoms, said cycloaliphatic ring being fused to the imidazble    ring through an adjacent ring substituent, and a cycloaromatic ring    comprising at least about 6 carbon atoms, said cycloaromatic ring    being fused to the imidazole ring through an adjacent ring    substituent. In one exemplary embodiment, in the structures (I),    (II), (III), (IV) and/or (V) above, X is the same as the linking    functionality Y.

The following examples are included to provide additional guidance tothose skilled in the art in practicing the claimed disclosure. Theexamples provided are merely representative of the present disclosure.Accordingly, the following examples are not intended to limit thedisclosure, as defined in the appended claims, in any manner.

Examples in Table 1: For each of the examples listed in Table 1, thefollowing synthetic procedure was used to prepare the catalyst with thepromoters listed in Table 1. About 30 mg to about 55 mg of dry Rohm andHaas A131 resin beads (sulfonated polystyrene, cross linked with about4% divinylbenzene) with about 4 times it's mass of molten phenol wereheated at about 70° C. for about one hour. To this mixture was added a540 mM phenol solution of the promoter, in an amount sufficient to yielda reaction mixture, which was about 1 mmole of promoter per gram of dryresin. The resulting reaction mixture was stirred for about 4 hours,after which time a portion of the phenol was removed. The resultingmixture of catalyst in phenol had a mass of about 3.5 times the mass ofthe initial dry resin. To demonstrate the catalytic activity of thecatalyst prepared by the procedure described above, a condensationreaction was performed by feeding a solution of about 9 wt % acetone inphenol, while maintaining a reactor temperature of 70° C. in anincremental flow reactor run at a space velocity of about 2.7 mg feed/mgdry resin/hr and a liquid residence time of about 0.9 hr. After about 40cycles of alternate feeding and reactor mixture removal, the compositionin the reactor was near steady state and samples were taken and analyzedfor 4,4′-isopropylidenediphenol (p,p-BPA), and4,2′-isopropylidenediphenol (o,p-BPA),) and eight other compounds knownto sometimes be formed in smaller amounts. Table 1 summarizes theresults by tabulating the wt % p,p-BPA produced, and the ratio of pp-BPAto o,p-BPA (“pp/op ratio”) and the overall pp-BPA selectivity, which isdefined as the weight % p,p-BPA as a fraction of all products measured.

TABLE 1 Formation of pp-BPA, using a 9% acetone in phenol solution, at70° C. for 1 hour, catalyzed by Rohm & Haas A131 resin (1 meq/g, 19%neutralized), functionalized with the following attached promoters. avgavg avg stdev stdev stdev pp/op pp-BPA pp-BPA pp/op pp-BPA pp-BPAattached promoter ratio selectivity wt % % yield ratio selectivity wt %2-(3′-tert-butylthiopropylthioethyl)pyridine 46.37 95.75 24.80 70.1 1.660.01 0.92 2-(6′-tert-butylthiohexylthio)-pyridine 49.12 95.73 27.86 78.70.36 0.08 1.38 4-(6′-tert-butylthiohexylthioethyl)pyridine 48.59 95.7329.94 84.6 1.58 0.08 5.21 2-(6′-tert-butylthiohexylthio)-benzothiazole46.19 95.70 24.33 68.8 0.78 0.03 0.232-(4′-tert-butylthiobutylthio)-pyridine 47.31 95.65 26.30 74.3 0.34 0.010.34 2-(5′-tert-butylthiopentylthio)-benzothiazole 47.28 95.65 25.9573.3 2.06 0.03 2.34 4-(4′-tert-butylthiobutylthioethyl)pyridine 48.6795.65 25.96 73.4 0.62 0.10 0.524-(5′-tert-butylthiopentylthioethyl)pyridine 45.27 95.62 27.96 79.0 0.400.08 2.87 2-(5′-tert-butylthiopentylthio)-pyridine 51.42 95.62 27.7178.3 1.17 0.02 0.16 2-(3′-tert-butylthiopropylthio)pyridine 41.58 95.5323.71 67.0 1.02 0.01 0.51 4-(3′-tert-butylthiopropylthioethyl)pyridine46.01 95.50 23.24 65.7 0.26 0.03 1.491-methyl-2-(3′-tert-butylthiopropylthio)imidazole 41.85 95.42 21.99 62.20.86 0.03 0.47 4-(3′-tert-butylthiopropylthio)pyridine 39.18 95.39 21.3460.3 0.18 0.05 0.14 2-(6′-tert-butylthiohexylthio)-benzimidazole 44.4995.39 23.97 67.7 0.73 0.00 0.042-(4′-tert-butylthiobutylthio)-benzothiazole 40.02 95.38 22.48 63.5 0.010.00 1.17 2-(5′-tert-butylthiopentylthio)-benzimidazole 45.41 95.3422.65 64.0 0.31 0.07 1.546-ethoxy-2-(3′-tert-butylthiopropylthio)benzothiazole 38.11 95.31 21.6361.1 1.16 0.14 0.28 2-(4′-tert-butylthiobutylthio)-benzimidazole 42.7795.29 23.53 66.5 2.59 0.00 8.952-(3′-tert-butylthiopropylthio)benzothiazole 37.64 95.19 21.95 62.0 0.630.05 0.87 2-(3′-tert-butylthiopropylthio)benzimidazole 38.40 95.12 22.0962.4 0.64 0.01 1.56 4-tert-butyl-thiomethylbenzyl amine, carbon dioxidecomplex 38.50 95.06 23.52 66.5 1.47 0.00 0.645-methyl-2-(3′-tert-butylthiopropylthio)benzimidazole hydrochloride37.37 95.05 22.17 62.7 2.52 0.09 0.23 4-pyridyl ethyl mercaptan 33.8294.98 22.64 64.0 0.26 0.14 1.39 2-(2′-tert-butylthioethyl)pyridine 32.0794.85 26.89 76.0 0.53 0.11 0.30 5-mercaptopentylamine hydrochloride38.10 94.82 27.18 76.8 0.55 0.52 0.161-(3′-tert-butylthiopropyl)-1,3-dihydro-benzimidazole-2-one 27.21 94.1321.50 60.8 0.82 0.08 1.47 4-tert-butyl-thiomethylbenzyl triethylammonium chloride 24.58 93.90 18.77 53.1 0.03 0.10 0.30

From the results presented in Table 1, it is evident that the catalystsprepared by the method of the present disclosure using the attachedpromoters listed in Table 1, can effectively catalyze the formation ofpp-BPA from phenol and acetone. For comparison, when Rohm and Haas A131resin beads are used under similar conditions as described above, butwithout an attached promoter, the p,p-BPA produced amounts to about 9.9wt %, with a pp selectivity of about 83.8%, and a pp/op ratio of about7.5. Furthermore, when Rohm and Haas A131 resin beads are used undersimilar conditions as described above, except with a tert-butoxycarbonyl sulfur protected cysteamine promoter, the p,p-BPA producedamounts to about 22.5 wt %, with a pp selectivity of about 93.7%, and app/op ratio of about 23.9.

While the disclosure has been illustrated and described, it is notintended to be limited to the details shown, since various modificationsand substitutions can be made without departing in any way from thespirit of the present invention. As such, further modifications andequivalents of the disclosure herein disclosed can occur to personsskilled in the art using no more than routine experimentation, and allsuch modifications and equivalents are believed to be within the spiritand scope of the disclosure as defined by the following claims.

1. A method for producing a catalyst composition which catalyzes theformation of bisphenols from aromatic hydroxy compounds and carbonylcontaining compounds, said method comprising the step of attaching apoly-sulfur mercaptan promoter component to a solid acid supportcomponent comprising a protic acid functionality, said poly-sulfurmercaptan promoter component having the following structure (I),

wherein R₁ is a benzimidazole functionality; wherein a is between about0 and about 11; wherein b is between about 1 and about 11; wherein c isbetween about 1 and about 11; wherein d is between about 1 and about 5;wherein X is a linking functionality which is one member selected fromthe group consisting of a linear aliphatic chain comprising betweenabout 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising atleast 5 carbon atoms, a cyclic aromatic ring comprising at least 6carbon atoms, a cyclic aliphatic heterocycle comprising at least 3carbon atoms, and a cyclic aromatic heterocycle comprising at least 3carbon atoms; wherein Y is a linking functionality which is one memberselected from the group consisting of a linear aliphatic chaincomprising between about 1 and about 11 carbon atoms, a cyclic aliphaticring comprising at least 5 carbon atoms, a cyclic aromatic ringcomprising at least 6 carbon atoms, a cyclic aliphatic heterocyclecomprising at least 3 carbon atoms, and a cyclic aromatic heterocyclecomprising at least 3 carbon atoms; and wherein R₂ is one memberselected from the group consisting of a hydrogen, a secondary aliphaticfunctionality, a tertiary aliphatic functionality, an esterfunctionality, a carbonate functionality, and a benzyl functionalitywhich is attached via the benzylic methylene carbon.
 2. The method ofclaim 1, wherein said tertiary aliphatic functionality is one memberselected from the group consisting of a branched aliphaticfunctionality, and a cyclic aliphatic functionality.
 3. The method ofclaim 1, wherein said R₂ functionality is one member selected from thegroup consisting of an isopropyl functionality, an isobutylfunctionality, a tertiary butyl functionality, a tertiary amylfunctionality, a cyclopentyl functionality, a benzyl, a 4-methoxybenzylfunctionality, a 1-methylcyclohexyl functionality, and a cyclohexylfunctionality.
 4. The method of claim 1, wherein said esterfunctionality is one member selected from the group consisting of anacetate functionality, a propionate functionality, and a benzoatefunctionality.
 5. The method of claim 1, wherein said carbonatefunctionality is one member selected from the group consisting of analkyl carbonate functionality, and an aromatic carbonate functionality.6. The method of claim 1, wherein the bisphenol which is being formed is4,4′-isopropylidenediphenol.
 7. The method of claim 1, wherein thecarbonyl containing compound is a ketone or an aldehyde.
 8. The methodof claim 1, wherein the aromatic hydroxy compound is phenol, and thecarbonyl containing compound is acetone.
 9. The method of claim 1,wherein the attachment step is performed in an aqueous solutioncomprising water.
 10. The method of claim 1, wherein said solid acidcomprises at least one member selected from the group consisting ofpolystyrene, a zeolite, and silica.
 11. A method for producing acatalyst composition which catalyzes the formation of bisphenols fromaromatic hydroxy compounds and carbonyl containing compounds, saidmethod comprising the step of attaching a poly-sulfur mercaptan promotercomponent to a polymeric resin component comprising a protic acidfunctionality, wherein said poly-sulfur mercaptan promoter component isa functionalized benzimidazole mercaptan.
 12. The method of claim 11,wherein said a functionalized benzimidazole mercaptan has the structure(III),

wherein i is between about 0 and about 11; wherein j is between about 1and about 11; wherein k is between about 1 and about 11; wherein R₉ is ahydrogen atom or a sulfur-protecting functionality which is one memberselected from the group consisting of an aliphatic functionalitycomprising at least about 4 carbon atom, an ester functionalitycomprising about 1 and about 11 carbon atoms, a carbonate functionalitycomprising between about 1 and about 11 carbon atoms, and a benzylicfunctionality comprising at least about 7 carbon atoms which is attachedto the terminal sulfur atom via the benzylic methylene carbon; whereinR₁₀ is one member selected from the group consisting of a hydrogen, analiphatic carbonyl functionality comprising about 1 to about 11 carbonatoms, an aliphatic functionality comprising between about 1 and about11 carbon atoms, an aromatic carbonyl functionality comprising at leastabout 7 carbon atoms, and an aromatic functionality comprising at leastabout 6 carbon atoms; wherein each of R₁₁, R₁₂, R₁₃ and R₁₄ areindependently one member selected from the group consisting of ahydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, ahydroxide, an alkoxide functionality comprising between about 1 andabout 11 carbon atoms, an aryloxide functionality comprising at leastabout 6 carbon atoms, an aliphatic functionality comprising betweenabout 1 and about 11 carbon atoms, an aromatic functionality comprisingat least about 6 carbon atoms, a cycloaliphatic ring comprising at leastabout 5 carbon atoms, said cycloaliphatic ring being fused to thebenzimidazole arene ring through an adjacent ring substituent, and acycloaromatic ring comprising at least about 6 carbon atoms, saidcycloaromatic ring being fused to the benzimidazole arene ring throughan adjacent ring substituent; wherein X is a linking functionality whichis selected from the group consisting of a linear aliphatic chaincomprising between about 1 and about 11 carbon atoms, a cyclic aliphaticring comprising at least 5 carbon atoms, a cyclic aromatic ringcomprising at least 6 carbon atoms, a cyclic aliphatic heterocyclecomprising at least 3 carbon atoms, and a cyclic aromatic heterocyclecomprising at least 3 carbon atoms; and wherein Y is a linkingfunctionality which is selected from the group consisting of a linearaliphatic chain comprising between about 1 and about 11 carbon atoms, acyclic aliphatic ring comprising at least 5 carbon atoms, a cyclicaromatic ring comprising at least 6 carbon atoms, a cyclic aliphaticheterocycle comprising at least 3 carbon atoms, and a cyclic aromaticheterocycle comprising at least 3 carbon atoms.
 13. The method of claim11, wherein the bisphenol which is being formed is4,4′-isopropylidenediphenol.
 14. The method of claim 11, wherein thecarbonyl containing compound is a ketone or an aldehyde.
 15. The methodof claim 11, wherein the aromatic hydroxy compound is phenol, and thecarbonyl containing compound is acetone.
 16. The method of claim 11,wherein the attachment step is performed in an aqueous solutioncomprising water.
 17. The method of claim 11, wherein said polymericresin comprises at least one member selected from the group consistingof polystyrene, a zeolite, and silica.
 18. The method of claim 17,wherein said polymeric resin further comprises divinylbenzene.
 19. Themethod of claim 18, wherein the amount of divinylbenzene is up to about12 percent of the total weight of the polymeric resin.
 20. The method ofclaim 11, wherein said protic acid functionality comprises at least onemember selected from the group consisting of a sulfonic acidfunctionality, a phosphonic acid functionality, and a carboxylic acidfunctionality.
 21. The method of claim 12, wherein the linkingfunctionality X, is the same as the linking functionality Y.
 22. Themethod of claim 12, wherein the bisphenol is4,4′-isopropylidenediphenol, the aromatic hydroxy compound is phenol,the carbonyl containing compound is acetone, and said promoter componentis,

wherein R₃₀ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon.
 23. Themethod of claim 12, wherein the bisphenol is4,4′-isopropylidenediphenol, the aromatic hydroxy compound is phenol,the carbonyl containing compound is acetone, and said promoter componentis,

wherein R₃₁ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon.
 24. Themethod of claim 12, wherein the bisphenol is4,4′-isopropylidenediphenol, the aromatic hydroxy compound is phenol,the carbonyl containing compound is acetone, and said promoter componentis,

wherein R₃₂ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached via the benzylic methylene carbon.
 25. A methodfor forming bisphenols, comprising the step of reacting an aromatichydroxy compound with a carbonyl containing compound in the presence ofa catalyst composition, said catalyst composition comprising a solidacid component and a poly-sulfur mercaptan promoter component having thefollowing structure (I),

wherein R₁ is a benzimidazole functionality; wherein a is between about0 and about 11; wherein b is between about 1 and about 11; wherein c isbetween about 1 and about 11; wherein d is between about 1 and about 5;wherein X is a linking functionality which is one member selected fromthe group consisting of a linear aliphatic chain comprising betweenabout 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising atleast 5 carbon atoms, a cyclic aromatic ring comprising at least 6carbon atoms, a cyclic aliphatic heterocycle comprising at least 3carbon atoms, and a cyclic aromatic heterocycle comprising at least 3carbon atoms; wherein Y is a linking functionality which is one memberselected from the group consisting of a linear aliphatic chaincomprising between about 1 and about 11 carbon atoms, a cyclic aliphaticring comprising at least 5 carbon atoms, a cyclic aromatic ringcomprising at least 6 carbon atoms, a cyclic aliphatic heterocyclecomprising at least 3 carbon atoms, and a cyclic aromatic heterocyclecomprising at least 3 carbon atoms; and wherein R₂ is one memberselected from the group consisting of a hydrogen, a secondary aliphaticfunctionality, a tertiary aliphatic functionality, an esterfunctionality, a carbonate functionality, and a benzyl functionalitywhich is attached via the benzylic methylene carbon.
 26. The method ofclaim 25, wherein said tertiary aliphatic functionality is one memberselected from the group consisting of a branched aliphaticfunctionality, and a cyclic aliphatic functionality.
 27. The method ofclaim 25, wherein said R₂ is one member selected from the groupconsisting of a, an isopropyl functionality, an isobutyl functionality,a tertiary butyl functionality, a tertiary amyl functionality, acyclopentyl functionality, a benzyl, a 4-methoxybenzyl, a1-methylcyclohexyl functionality, and a cyclohexyl functionality. 28.The method of claim 25, wherein said ester functionality is one memberselected from the group consisting of an acetate functionality, apropionate functionality, and a benzoate functionality.
 29. The methodof claim 25, wherein said carbonate functionality is one member selectedfrom the group consisting of an alkyl carbonate functionality, and anaromatic carbonate functionality.
 30. The method of claim 25, whereinthe bisphenol which is being formed is 4,4′-isopropylidenediphenol. 31.The method of claim 25 wherein the aromatic hydroxy compound is phenol.32. The method of claim 25, wherein the carbonyl containing compound isa ketone or an aldehyde.
 33. The method of claim 32 wherein the ketoneis acetone.
 34. The method of claim 25, wherein said solid acidcomprises at least one member selected from the group consisting ofpolystyrene, a zeolite, and silica.
 35. The method of claim 25 whereinsaid solid acid is a sulfonic acid functionalized polymeric resin. 36.The method of claim 35, wherein said polymeric resin further comprisesdivinylbenzene.
 37. The method of claim 36, wherein the amount ofdivinylbenzene is up to about 12 percent of the total weight of thepolymeric resin.
 38. The method of claim 25 wherein said solid acidcomponent comprises at least one member selected from the groupconsisting of a sulfonic acid functionality, a phosphonic acidfunctionality, and a carboxylic acid functionality.
 39. The method ofclaim 25, wherein the linking functionality X, is the same as thelinking functionality Y.
 40. A method for forming bisphenols, comprisingthe step of reacting an aromatic hydroxy compound with a carbonylcontaining compound in the presence of a catalyst composition, saidcatalyst composition comprising a polymeric resin component comprising aprotic acid functionality, and a poly-sulfur mercaptan promotercomponent, wherein said poly-sulfur mercaptan promoter component is afunctionalized benzimidazole mercaptan.
 41. The method of claim 40,wherein said functionalized benzimidazole mercaptan has the structure(III),

wherein i is between about 0 and about 11; wherein j is between about 1and about 11; wherein k is between about 1 and about 11; wherein R₉ is ahydrogen atom or a sulfur-protecting functionality which is one memberselected from the group consisting of an aliphatic functionalitycomprising at least about 4 carbon atom, an ester functionalitycomprising between about 1 and about 11 carbon atoms, a carbonatefunctionality comprising between about 1 and about 11 carbon atoms, anda benzylic functionality comprising at least about 7 carbon atoms whichis attached to the terminal sulfur atom via the benzylic methylenecarbon; wherein R₁₀ is one member selected from the group consisting ofa hydrogen, an aliphatic carbonyl functionality comprising about 1 toabout 11 carbon atoms, an aliphatic functionality comprising betweenabout 1 and about 11 carbon atoms, an aromatic carbonyl functionalitycomprising at least about 7 carbon atoms, and an aromatic carbonylfunctionality comprising at least about 6 carbon atoms; wherein each ofR₁₁, R₁₂, R₁₃ and R₁₄ are independently one member selected from thegroup consisting of a hydrogen, a fluoride, a bromide, a chloride, aniodide, a vinyl group, a hydroxide, an alkoxide functionality comprisingbetween about 1 and about 11 carbon atoms, an aryloxide functionalitycomprising at least about 6 carbon atoms, an aliphatic functionalitycomprising between about 1 and about 11 carbon atoms, an aromaticfunctionality comprising at least about 6 carbon atoms, a cycloaliphaticring comprising at least about 5 carbon atoms, said cycloaliphatic ringbeing fused to the benzimidazole arene ring through an adjacent ringsubstituent, and a cycloaromatic ring comprising at least about 6 carbonatoms, said cycloaromatic ring being fused to the benzimidazole arenering through an adjacent ring substituent; wherein X is a linkingfunctionality which is selected from the group consisting of a linearaliphatic chain comprising between about 1 and about 11 carbon atoms, acyclic aliphatic ring comprising at least 5 carbon atoms, a cyclicaromatic ring comprising at least 6 carbon atoms, a cyclic aliphaticheterocycle comprising at least 3 carbon atoms, and a cyclic aromaticheterocycle comprising at least 3 carbon atoms; and wherein Y is alinking functionality which is selected from the group consisting of alinear aliphatic chain comprising between about 1 and about 11 carbonatom, a cyclic aliphatic ring comprising at least 5 carbon atoms, acyclic aromatic ring comprising at least 6 carbon atoms, a cyclicaliphatic heterocycle comprising at least 3 carbon atoms, and a cyclicaromatic heterocycle comprising at least 3 carbon atoms.
 42. The methodof claim 40, wherein the bisphenol which is being formed is4,4′-isopropylidenediphenol.
 43. The method of claim 40, wherein thearomatic hydroxy compound is phenol.
 44. The method of claim 40, whereinthe carbonyl containing compound is a ketone or an aldehyde.
 45. Themethod of claim 44, wherein the ketone is acetone.
 46. The method ofclaim 40, wherein said polymeric resin comprises at least one memberselected from the group consisting of polystyrene, a zeolite, andsilica.
 47. The method of claim 46, wherein said polymeric resin furthercomprises divinylbenzene.
 48. The method of claim 47, wherein the amountof divinylbenzene is up to about 12 percent based on the total weight ofthe polymeric resin.
 49. The method of claim 40, wherein said proticacid functionality comprises at least one member selected from the groupconsisting of a sulfonic acid functionality, a phosphonic acidfunctionality, and a carboxylic acid functionality.
 50. The method ofclaim 41, wherein the linking functionality X, is the same as thelinking functionality Y.
 51. The method of claim 41, wherein thebisphenol is 4,4′-isopropylidenediphenol, the aromatic hydroxy compoundis phenol, the carbonyl containing compound is acetone, and saidpromoter component is,

wherein R₃₀ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached to the terminal sulfur atom via the benzylicmethylene carbon.
 52. The method of claim 41, wherein the bisphenol is4,4′-isopropylidenediphenol, the aromatic hydroxy compound is phenol,the carbonyl containing compound is acetone, and said promoter componentis,

wherein R₃₁ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached to the terminal sulfur atom via the benzylicmethylene carbon.
 53. The method of claim 41, wherein the bisphenol is4,4′-isopropylidenediphenol, the aromatic hydroxy compound is phenol,the carbonyl containing compound is acetone, and said promoter componentis,

wherein R₃₂ is a hydrogen atom or a sulfur-protecting functionalitywhich is one member selected from the group consisting of an aliphaticfunctionality comprising at least about 4 carbon atom, an esterfunctionality comprising between about 1 and about 11 carbon atoms, acarbonate functionality comprising between about 1 and about 11 carbonatoms, and a benzylic functionality comprising at least about 7 carbonatoms which is attached to the terminal sulfur atom via the benzylicmethylene carbon.
 54. A benzimidazole compound having following thestructure (III),

wherein i is between about 0 and about 11; wherein j is between about 1and about 11; wherein k is between about 1 and about 11; wherein R₉ is ahydrogen atom or a sulfur-protecting functionality which is one memberselected from the group consisting of an aliphatic functionalitycomprising at least about 4 carbon atom, an ester functionalitycomprising between about 1 and about 11 carbon atoms, a carbonatefunctionality comprising between about 1 and about 11 carbon atoms, anda benzylic functionality comprising at least about 7 carbon atoms whichis attached to the terminal sulfur atom via the benzylic methylenecarbon; wherein R₁₀ is one member selected from the group consisting ofa hydrogen, an aliphatic carbonyl functionality comprising about 1 toabout 11 carbon atoms, an aliphatic functionality comprising betweenabout 1 and about 11 carbon atoms, an aromatic carbonyl functionalitycomprising at least about 7 carbon atoms, and an aromatic functionalitycomprising at least about 6 carbon atoms; wherein each of R₁₁, R₁₂, R₁₃and R₁₄ are independently one member selected from the group consistingof a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinylgroup, a hydroxide, an alkoxide functionality comprising between about 1and about 11 carbon atoms, an aryloxide functionality comprising atleast about 6 carbon atoms, an aliphatic functionality comprisingbetween about 1 and about 11 carbon atoms, an aromatic functionalitycomprising at least about 6 carbon atoms, a cycloaliphatic ringcomprising at least about 5 carbon atoms, said cycloaliphatic ring beingfused to the benzimidazole arene ring through an adjacent ringsubstituent, and a cycloaromatic ring comprising at least about 6 carbonatoms, said cycloaromatic ring being fused to the benzimidazole arenering through an adjacent ring substituent; wherein X is a linkingfunctionality which is selected from the group consisting of a linearaliphatic chain comprising between about 1 and about 11 carbon atoms, acyclic aliphatic ring comprising at least 5 carbon atoms, a cyclicaromatic ring comprising at least 6 carbon atoms, a cyclic aliphaticheterocycle comprising at least 3 carbon atoms, and a cyclic aromaticheterocycle comprising at least 3 carbon atoms; and wherein Y is alinking funtionality which is selected from the group consisting of alinear aliphatic chain comprising between about 1 and about 11 carbonatoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, acyclic aromatic ring comprising at least 6 carbon atoms, a cyclicaliphatic heterocycle comprising at least 3 carbon atoms, and a cyclicaromatic heterocycle comprising at least 3 carbon atoms.